CN102229593A - Method for preparing natural vitamin E from crude oil of Maoyeshan tung tree seed - Google Patents
Method for preparing natural vitamin E from crude oil of Maoyeshan tung tree seed Download PDFInfo
- Publication number
- CN102229593A CN102229593A CN2011102084563A CN201110208456A CN102229593A CN 102229593 A CN102229593 A CN 102229593A CN 2011102084563 A CN2011102084563 A CN 2011102084563A CN 201110208456 A CN201110208456 A CN 201110208456A CN 102229593 A CN102229593 A CN 102229593A
- Authority
- CN
- China
- Prior art keywords
- crude oil
- vitamin
- ethyl acetate
- maoyeshan
- silica gel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention discloses a method for separating, purifying and preparing natural vitamin E from crude oil of Maoyeshan tung tree seed, which belongs to the field of medicines, foods and feeds. The method mainly comprises the steps of preparing through a chromatographic column, eluting and concentrating a solvent, treating active carbon, decompressing, drying and the like, wherein the vitamin E in the crude oil of the Maoyeshan tung tree seed can be directly eluted, separated and purified by using the chromatographic column and a petroleum ether-ethyl acetate system through a low-pressure chromatography; after being concentrated properly, the vitamin E is treated by the active carbon; and a high-quality natural vitamin E product can be obtained by being dried at low temperature in a vacuum way. The method has the advantages that: the content of the vitamin E in the crude oil can be directly improved from about 0.1% to above 70% through a few operation steps; simultaneously, the process is simple and has a few operation steps and low equipment requirement; a high-temperature heating process is unnecessary; the separation residue can be used in other purposes of the oil of the Maoyeshan tung tree seed; the method is applicable for enterprises of different scales to product; and the method has a wide application prospect.
Description
Technical field
The invention belongs to medicine, food and field of fodder, particularly a kind of is the method for raw material production natural VE with the Idesia polycarpa crude oil.
Background technology
Idesia polycarpa is the distinctive woody oleiferous plants plant variety of China, have widely distributed, less demanding to soil, weather etc., the characteristics that adaptability is stronger, be suitable for low quality, barren hill, beach, mountain planting has the characteristics of " easily cultivate, easily promote, easily popularize ".The cash crop that it is a kind of high yield, economic worth is high have great using value and potentiality to be exploited.According to document announcement: Idesia polycarpa reaches 70～100 years the period of growth of the crop, its fruit oleaginousness is higher, and (the individual plant produce oil can reach 200～300kg), especially its oily unsaturated fatty acids is up to more than 82%, and is rich in linolic acid (up to 68～80%) and vitamin-E (more than 1110mg/kg).
Vitamin-E is distributed widely in the vegetable and animals oils, is one of necessary VITAMIN of human body, and people and animal self can not synthesize, and can only absorb from food.The vitamin-E product is widely used in medicine, food, cosmetic industry.It has anti-oxidant, removing free radical, anticancer, anti-cardiovascular disease, raising immunizing power and antidotal effect, all there is good health-care medical to be worth to diseases such as arteriosclerosis, coronary heart disease, habitual abortion, woman's acyesis, endocrine dysfunction decline, hepatopathys, also be a kind of ideal functional health nutrient fortified food composition and antioxidant simultaneously, and be to fowl poultry immune, diseases prevention and treatment, improve aspects such as meat the fodder additives of vital role arranged, and have and improve the wait for a long time makeup additive of specific function of skin elasticity, beauty treatment, skin care, health care.2000 so far, and the demand of vitamin-E is with 10%～15% speed increment in the world wide.Although the market value of synthetic vitamin-E is more much lower than natural product at present, along with people's health care consciousness strengthens, natural vitamin E product is just presenting the development trend that replaces synthetics gradually.
The plantation Idesia polycarpa, not only can improve the ecological environment, and its product can also be used for the machining of special nutrient health care edible oil and extract natural VE, is a kind of ideal high-quality oil crops and natural VE source, and the market development prospect is very wide.
At present, industrial preparation natural VE mainly is to be raw material with the vegetable fat deodorizing effluent, and its separation purification method mainly contains extraction process (organic solvent extraction and supercritical CO
2Extraction), distillation method (simple distillation and molecular distillation), urea complexation and chromatography (silica gel or gel absorption method, high performance liquid chromatography or low-pressure column chromatography method, ion chromatography etc.).But the natural vitamin E product with organic solvent extractionprocess, urea complexation and distillation method obtain causes biological activity to be hanged down because of purity is low and can not satisfy pharmaceuticals and the growing demand of health-product market; And supercritical CO
2The facility investment of extraction process and molecular distillation method is bigger; The chromatography separating power is strong, can not only separate to obtain highly purified mixing vitamin E, can also obtain the graded product of vitamin-E; But wherein the high performance liquid chromatography facility investment is big, and the maintenance cost height is not suitable for large-scale industrial production.And the low-pressure column chromatography method has preferably separating power and production cost is lower.
This patent is to be raw material with the Idesia polycarpa crude oil, adopts low-pressure column chromatography method and petroleum ether-ethyl acetate system, and directly separation and purification prepares the novel method of natural VE from crude oil.It will realize effectively developing Idesia polycarpa oil, increase the market supply of natural VE, satisfy people's productive life demand, will bring higher production added value and economic benefit to plantation peasant household and enterprise simultaneously, have very important realistic meaning and strategic importance.
Summary of the invention
The objective of the invention is to utilize Idesia polycarpa crude oil after the squeeze and filter removal of impurities to prepare the method for natural VE.This method is utilized the low-pressure chromatography post, adopts the petroleum ether-ethyl acetate system directly to separate the preparation vitamin-E from the Idesia polycarpa crude oil, has higher yield and purity, collects isolating remaining thing and still can make his usefulness in addition.The advantage of this method is the content of vitamin-E in the crude oil is brought up to more than 70% from about 0.1%.Simultaneously, it is low for equipment requirements, the working condition gentleness, need not heat, power consumption less, technology can operate by force, suitable large-scale production.
The present invention is realized by following technical proposals.This scheme comprises that mainly chromatographic column preparation, solvent elution, activated carbon treatment, drying under reduced pressure, collection separate technological processs such as remaining thing.It is characterized in that:
(1) an amount of 100～300 purpose silica gel is loaded on post directly than in 5: 1～10: 1 chromatographic column with the sherwood oil wet method.
(2) the Idesia polycarpa crude oil of silica gel amount 8-12% is added on the top of chromatographic column, with petroleum ether-ethyl acetate system (sherwood oil: the ethyl acetate scope is in 80: 1～50: 1) wash-out under the flow conditions of 3～6mL/min, collect the effluent liquid in the 2nd～10th the crude oil volume range, and, obtain about 2mL oily and just divide thing in 20～40 ℃ of concentrating under reduced pressure to no moving phase.
(3) an amount of 200～400 purpose silica gel are loaded on post directly than in 10: 1～20: 1 chromatographic column with the sherwood oil wet method.
(4) the first minute thing of silica gel amount 1-2% is added on the top of chromatographic column, with petroleum ether-ethyl acetate system (sherwood oil: the ethyl acetate scope is in 110: 1～80: 1) wash-out under the flow conditions of 1～4mL/min, collect the effluent liquid in the 2nd～4th the crude oil volume range, and in about 20～40 ℃ of concentrating under reduced pressure to 50～100mL.
(5) will just divide the gac of thing consumption 0.25～1 times (w/v) to join in the concentrated solution, at room temperature stir 15～20h,, filtrate at 20～40 ℃ of drying under reduced pressure 25～35min, be got high-quality vitamin-E with 200 purpose filter clothes or 0.45 μ m membrane filtration.
(6) will isolate remaining part on the post of vitamin-E, with 3-8 column volume of washing with alcohol, behind the decompression recycling ethanol, yellow oil, this oily matter still can be used as Idesia polycarpa oil and makes his usefulness in addition.
The method that Idesia polycarpa crude oil provided by the invention prepares vitamin-E has following remarkable advantage: utilize the Idesia polycarpa crude oil after the squeeze and filter removal of impurities to be raw material, adopt the low-pressure chromatography post, with petroleum ether-ethyl acetate system wash-out and decolorizing with activated carbon, drying under reduced pressure can obtain high-quality natural VE by the direct separation and purification of chromatography, its advantage is the content of vitamin-E in the crude oil is brought up to more than 70% from 0.1%, and the easy economy of preparation process, operation steps is few, workable, need not heat, not high to equipment requirements, the agents useful for same major part can recycling, economic environmental protection; The product of producing is suitable for application such as medicine, healthcare products, separates remaining thing and still can be used as Idesia polycarpa oil do his in addition and use behind ethanol elution; The enterprise that is fit to different scales produces, and has the good application and the market requirement.
Below to the detailed description of the invention:
Gordian technique of the present invention have following some:
The one, 2 petroleum ether-ethyl acetate eluent system that adopt (are sherwood oil: ethyl acetate=80: 1～50: 1 for the first time, be sherwood oil for the second time: ethyl acetate=110: 1～80: 1) suitable, otherwise separating effect is bad, and purity is low, yield is low, foreign matter content is high.
Two is that the capture range of 2 wash-out effluent liquid is (for the first time for collecting the 2nd～10th raw material consumption volume range, for the second time for collecting the 2nd～4th raw material consumption volume range) and the silica gel consumption (be 8～13 times of raw material consumptions for the first time, be 50～100 times of raw material consumptions for the second time) to suit, the narrow then yield of effluent liquid capture range is low, and the wide then purity of scope is low, foreign matter content is high; It is few or foreign matter content is high that the silica gel consumption is crossed low then recovery rate, and consumption crosses at most that silica gel and eluent use cost increase the subsequent operations difficulty.
The 3rd, consumption of gac (0.25～1 times (w/v) just dividing the thing consumption) and treatment time, it is short that consumption reaches the treatment time less, the purpose of all can not reach effective decolouring, taking off impurity, and consumption increases cost at most, subsequent technique work of treatment amount is big.
The 4th, filtrate filtered processing mode (temperature, time), do not adopt activated carbon treatment then purity be low, foreign matter content is high, peculiar smell is arranged, variegated, the too high then vitamin-E of temperature product is perishable, energy consumption increases, then purity is low, solvent removal is not thorough for the treatment time deficiency, long energy consumption and the workload of then increasing.
Embodiment
Following example will give further instruction to method provided by the invention.
Examples of implementation
(1) 2000 grams, 100～300 purpose silica gel are placed beaker, add about 1500mL sherwood oil, wet method is loaded on post directly than in 5: 1～10: 1 chromatographic column.
(2) the Idesia polycarpa crude oil with 200mL is added on the chromatographic column top, with sherwood oil: the system wash-out of ethyl acetate=75: 1, the control flow velocity is about 4.5mL/min, collect glassy yellow and yellowish green effluent liquid until saffron effluent liquid (effluent liquid of collected volume in 100mL～1000mL scope) occurring, and be evaporated to no moving phase in 30 ℃, obtain about 2mL oily and just divide thing.By this method repeatedly separation and purification obtain about 20mL oily and just divide thing.
(3) 1200 gram 200-400 purpose silica gel are placed beaker, add about 1000mL sherwood oil, wet method is loaded on post directly than 10: 1--20: in 1 the chromatographic column.
(4) first minute thing of 20mL dripped top in this chromatographic column, with sherwood oil: the system wash-out of ethyl acetate=99: 1, the control flow velocity is collected the effluent liquid in 100mL～300mL scope about 2.5mL/min, effluent liquid is evaporated to about 80mL at 20-40 ℃.
(5) gac with 15 grams joins in this liquid, at room temperature stirs 16h, with 0.45 μ m membrane filtration.At 30 ℃ of drying under reduced pressure 30min, get high-quality vitamin-E 2mL, the content of vitamin-E is 71.29% after testing.
(6) will isolate remaining part on the post of vitamin-E, with 6 column volumes of 95% washing with alcohol, behind the decompression recycling ethanol, yellow oil, this oily matter still can be used as Idesia polycarpa oil and utilizes.
Claims (3)
1. the preparation method of a natural VE is characterized in that utilizing the Idesia polycarpa crude oil after the squeeze and filter removal of impurities to prepare natural VE for basic raw material, and preparation process comprises:
(1) preparation silica gel chromatographic column.
(2) crude oil upper prop, with the direct wash-out of petroleum ether-ethyl acetate system, the effluent liquid of collecting pre-determined range obtains just dividing thing.
(3) will just divide thing again by silica gel chromatographic column and the direct wash-out of petroleum ether-ethyl acetate system, the effluent liquid of collecting pre-determined range obtains the vitamin-E isolate.
(4) the vitamin-E isolate is adopted activated carbon treatment, filtration after suitably concentrating.
(5) filtrate by low-temperature vacuum drying obtain high-quality vitamin-E.
(6) oily matter that remaining part on the post is obtained with ethanol elution and reclaim under reduced pressure is made his usefulness in addition.
2. according to the crude oil upper column quantity described in claim 1 step (2) and (3) and the petroleum ether-ethyl acetate eluent system of employing, it is characterized in that: the crude oil upper column quantity in the step (2) is 8～12% of a silica gel consumption; Eluent system PetroChina Company Limited. ether: the ratio range of ethyl acetate is 80: 1～50: 1, and elution flow rate is 3～7mL/min, and the volume range of collecting effluent liquid is the 2nd～10th times a crude oil volumetric usage).The crude oil upper column quantity is 1～2% of a silica gel consumption in the step (3); Eluent system PetroChina Company Limited. ether: the ratio range of ethyl acetate is 110: 1～80: 1, and elution flow rate is 1～4mL/min, and the volume range of collecting effluent liquid is the 1st～4th times a crude oil volumetric usage).
3. according to activated carbon treatment method in claim 1 step (4), it is characterized in that activated carbon dosage is 0.25～1 times raw material (just dividing a thing) consumption (w/v), stir 15～20h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102084563A CN102229593B (en) | 2011-07-25 | 2011-07-25 | Method for preparing natural vitamin E from crude oil of Maoyeshan tung tree seed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102084563A CN102229593B (en) | 2011-07-25 | 2011-07-25 | Method for preparing natural vitamin E from crude oil of Maoyeshan tung tree seed |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102229593A true CN102229593A (en) | 2011-11-02 |
| CN102229593B CN102229593B (en) | 2013-07-31 |
Family
ID=44842212
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102084563A Expired - Fee Related CN102229593B (en) | 2011-07-25 | 2011-07-25 | Method for preparing natural vitamin E from crude oil of Maoyeshan tung tree seed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102229593B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467432A (en) * | 2013-09-16 | 2013-12-25 | 四川省仁德制药有限公司 | Method for extracting vitamin E from deodorizer distillate of idesia polycarpa oil |
| CN104829582A (en) * | 2015-05-05 | 2015-08-12 | 陕西源邦生物技术有限公司 | Method for extracting high content natural vitamin E from annatto |
| CN106615673A (en) * | 2016-12-19 | 2017-05-10 | 四川大学 | Idesia polycarpa defatted cake meal fermented feed and preparation method thereof |
| CN106632211A (en) * | 2016-12-27 | 2017-05-10 | 四川贝泰妮生物科技有限公司 | Method for producing natural vitamin E by utilizing rice bran crude oil |
| CN111646970A (en) * | 2020-06-20 | 2020-09-11 | 四川中海茂农业开发有限公司 | Method for preparing natural vitamin E from deodorized distillate of idesia polycarpa crude oil |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106866607A (en) * | 2017-03-03 | 2017-06-20 | 四川森迪科技发展股份有限公司 | A kind of method that vitamin E is extracted in the oil cake from Idesia polycarpa |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040085981A (en) * | 2003-04-02 | 2004-10-08 | 한국생명공학연구원 | Melanin biosynthesis inhibiting compounds purified from Idesia polcarpa, and whitening compositions the same |
| CN101880601A (en) * | 2010-06-25 | 2010-11-10 | 四川省国政生物质能源科技发展股份有限公司 | Method for preparing linoleic acid from idesia polycarpa Maxium. Var. vestita Diels oil |
| CN102041167A (en) * | 2010-12-10 | 2011-05-04 | 四川省毛叶山桐子科技股份有限公司 | Method for preparing idesia polycarpa edible vegetable oil by immobilized enzyme and hot brine treatment process |
-
2011
- 2011-07-25 CN CN2011102084563A patent/CN102229593B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040085981A (en) * | 2003-04-02 | 2004-10-08 | 한국생명공학연구원 | Melanin biosynthesis inhibiting compounds purified from Idesia polcarpa, and whitening compositions the same |
| CN101880601A (en) * | 2010-06-25 | 2010-11-10 | 四川省国政生物质能源科技发展股份有限公司 | Method for preparing linoleic acid from idesia polycarpa Maxium. Var. vestita Diels oil |
| CN102041167A (en) * | 2010-12-10 | 2011-05-04 | 四川省毛叶山桐子科技股份有限公司 | Method for preparing idesia polycarpa edible vegetable oil by immobilized enzyme and hot brine treatment process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467432A (en) * | 2013-09-16 | 2013-12-25 | 四川省仁德制药有限公司 | Method for extracting vitamin E from deodorizer distillate of idesia polycarpa oil |
| CN103467432B (en) * | 2013-09-16 | 2016-08-17 | 四川省仁德制药有限公司 | A kind of method extracting vitamin E from deodorizer distillate of idesia polycarpa oil |
| CN104829582A (en) * | 2015-05-05 | 2015-08-12 | 陕西源邦生物技术有限公司 | Method for extracting high content natural vitamin E from annatto |
| CN106615673A (en) * | 2016-12-19 | 2017-05-10 | 四川大学 | Idesia polycarpa defatted cake meal fermented feed and preparation method thereof |
| CN106632211A (en) * | 2016-12-27 | 2017-05-10 | 四川贝泰妮生物科技有限公司 | Method for producing natural vitamin E by utilizing rice bran crude oil |
| CN111646970A (en) * | 2020-06-20 | 2020-09-11 | 四川中海茂农业开发有限公司 | Method for preparing natural vitamin E from deodorized distillate of idesia polycarpa crude oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102229593B (en) | 2013-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105535111B (en) | Numb medicinal extract of a kind of fire rich in cannabidiol and preparation method thereof | |
| CN102229593B (en) | Method for preparing natural vitamin E from crude oil of Maoyeshan tung tree seed | |
| CN101921254B (en) | Method for extracting natural vitamin E from blackberry seeds | |
| CN103333067B (en) | A kind of extracting method of high-purity chlorogenic acid | |
| CN103059075B (en) | A kind of production method of separation and purification rhodioside from Root of Kirilow Rhodiola | |
| CN102295983A (en) | Production method for comprehensive utilization of microalgae | |
| CN101774955A (en) | Method for preparing high-content trans-lutein crystals from dried marigold flower pellets | |
| CN102533433A (en) | Method for supercritical extraction of sea buckthorn oil | |
| CN102320953B (en) | Method for preparing natural alpha-linolenic acid from crude oil of idesia polycarpa var.vestita diels | |
| CN101449801A (en) | Lycopene extraction method from tomato peel | |
| CN103788218A (en) | Decomposition and extraction method of active ingredients in purple sweet potatoes | |
| CN101525558B (en) | Preparation process of functional polyunsaturated fatty acid in bee pollen | |
| CN104593441A (en) | Method for simultaneously extracting volatile oil, polysaccharides and amino acids from tricholoma matsutake | |
| CN107098942B (en) | Method for subcritical water extraction of kaempferitrin in radish leaves | |
| CN102327312A (en) | Method for extracting effective ingredients from leaf, stem and vine of honeysuckle | |
| CN1749253A (en) | Process for extracting proanthocyanidin from grape seed by super critical carbon dioxide | |
| CN103740460B (en) | Method for extracting and purifying grape seed oil from grape seeds | |
| CN103146472A (en) | Method for preparing eucommia seed oil by low-temperature cold-pressing technology | |
| CN104311616A (en) | Method for extracting high-purity esculine and fraxin from Cortex Fraxini | |
| CN101869586A (en) | Extracting method of high-purity taxol and derivative thereof | |
| CN103524589B (en) | Method for extracting and separating triterpenic acid and polyprenol from fir needle | |
| CN103191579B (en) | A kind of supercritical CO 2the method of gamma-Linolenic acid in extraction spirulina | |
| CN106317005B (en) | Method for extracting rose flavone from rose dreg water | |
| CN102669303B (en) | Preparation method for squalene-enriched tea oil | |
| CN105906738B (en) | The method of separating polyose is extracted in a kind of cockscomb |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHENGDU ACADEMY OF AGRICULTURE AND FORESTRY SCIENC Effective date: 20130717 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Tu Jie Inventor after: Feng Jun Inventor after: Li Juan Inventor after: Wang Qiao Inventor after: Zhang Zhengzhou Inventor after: Zheng Qi Inventor after: Zhang Hong Inventor after: Zhang Chisong Inventor after: Guo Qiliang Inventor after: Qin Dan Inventor after: Xiao Xiong Inventor after: Dong Pu Inventor after: Liu Jia Inventor before: Zheng Qi Inventor before: Tu Jie Inventor before: Zhang Hong Inventor before: Zhang Chisong Inventor before: Guo Qiliang Inventor before: Qin Dan Inventor before: Xiao Xiong Inventor before: Dong Pu |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: ZHENG QI TU JIE ZHANG HONG ZHANG CHISONG GUO QILIANG QIN DAN XIAO XIONG DONG PU TO: TU JIE ZHENG QI ZHANG HONG ZHANG CHISONG GUO QILIANG QIN DAN XIAO XIONG DONG PU LIU JIA FENG JUN LI JUAN WANG QIAO ZHANG ZHENGZHOU |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130717 Address after: 611930, Sichuan, Pengzhou province Fengzhen long village, Sichuan Run Green Agriculture Investment Co., Ltd. Industrial Park (inside) Patentee after: Sichuan Maoyeshan Dongzi Technology Co., Ltd. Patentee after: Chengdu Academy of Agriculture and Forestry Science Address before: 611930, Sichuan Pengzhou Sichuan Run Green Agricultural Investment Co., Ltd. Industrial Park (Fengzhen) Patentee before: Sichuan Maoyeshan Dongzi Technology Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130731 Termination date: 20150725 |
|
| EXPY | Termination of patent right or utility model |